1-(トリフルオロアセチル)ピペリジン(1)は，芳香環にトリフルオロアセチル基を導入する試薬として使われています。1は，アリールハライドのハロゲン－リチウム交換，芳香族化合物のオルトリチオ化等の方法で調製したアリールリチウムと低温下速やかに反応し，トリフルオロアセチル体を良好な収率で与えます。アリールGrignard試薬との反応も同様に進行しますが，アリールリチウムを用いる方法に比べるとその収率は低下する傾向があります。1は光親和性標識として有用なアリール（トリフルオロメチル）ジアジリンの合成において，ジアジリン骨格を導入する一連の反応に多く利用されています。

 

[1] “Ginkgolide Derivatives for Photolabeling Studies:? Preparation and Pharmacological Evaluation”

K. Stromgaard, D. R. Saito, H. Shindou, S. Ishii, T. Shimizu, K. Nakanishi, J. Med. Chem. 2002, 45, 4038. DOI: 10.1021/jm020147w

The terpene trilactones (TTLs), ginkgolides and bilobalide, are structurally unique constituents of Ginkgo biloba extracts, which exhibit various neuromodulatory properties. Although the TTLs are believed to be responsible for some of these effects, the specific interactions with targets in the central nervous system remain to be elucidated on a molecular level. Ginkgolides are known antagonists of the platelet-activating factor (PAF) receptor. Herein, we describe the first examination of the binding of native TTLs and their derivatives to the cloned PAF receptor, confirming that of the TTLs, ginkgolide B is the most potent PAF receptor antagonist. Ginkgolide derivatives carrying photoactivatable and fluorescent groups for the purpose of performing photolabeling have been prepared and evaluated using the cloned PAF receptor. These studies have shown that ginkgolide derivatives with aromatic photoactivatable substituents are potent PAF receptor antagonists with Ki values of 0.09−0.79 μM and hence excellent ligands for clarifying the binding of ginkgolides to PAF receptor by photolabeling studies. Ginkgolide derivatives incorporating both fluorescent and photoactivatable groups still retained binding affinity to the PAF receptor and hence should be promising ligands for photolabeling and subsequent sequencing studies.

[2] “Synthesis and Biological Evaluation of Photoaffinity Labeled Fusidic Acid Analogues”

D. Riber, M. Venkataramana, S. Sanyal, T. Duvold, J. Med. Chem. 2006, 49, 1503.　DOI: 10.1021/jm050583t

Novel photoaffinity labeled fusidic acid analogues were obtained by a synthetic sequence employing a Wittig reaction between a fusidic acid aldehyde and benzyl bromides in the key step. Three commonly used photoreactive groups, benzophenone, trifluoromethyldiazirine, and aryl azide, were used. The photoaffinity labeled fusidic acid analogues demonstrated a potent antibacterial activity (MIC 0.016−4 μg/mL) and therefore represent a potential tool for the elucidation of the interactions between fusidic acid and its receptor EF-G.

[3] “Comprehensive Synthesis of Photoreactive (3-Trifluoromethyl)diazirinyl Indole Derivatives from 5- and 6-Trifluoroacetylindoles for Photoaffinity Labeling”

Y. Murai, K. Masuda, Y. Sakihama, Y. Hashidoko, Y. Hatanaka, M. Hashimoto, J. Org. Chem. 2012, 77, 8581. DOI:10.1021/jo301552m

5- and 6-trifluoromethyldiazirinyl indoles were synthesized from corresponding bromoindole derivatives for the first time. They acted as mother skeletons for the comprehensive synthesis of various bioactive indole metabolites. These can be used in biological functional analysis as diazirine-based photoaffinity labels.

 

本品はジアジリン誘導体の合成で広く用いられています。その基本骨格となるフェニル基4-位にジアジリンを導入した光クロスリンカーもご用意しています。研究用途に合わせてお選びください。
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